The present invention relates to a plant diseases controlling composition and a plant diseases controlling method.
Various plant diseases controlling agents have been developed for controlling plant diseases, but a plant diseases controlling agent having higher activity is always requested.
The aim of a present invention is to provide a plant diseases controlling composition having high activity and a method for controlling efficiently plant diseases.
The present inventor has studied to control plant diseases, as a result, he has found that high synergistic effect for controlling plant diseases could be achieved by using some species of pyrazolinone derivatives and specific imide compounds together.
That is to say, the present invention provides a plant diseases controlling composition (hereinafter, referred to as the composition of the invention) comprising:
at least one imide compound selected from N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide (hereinafter, referred to as the Compound II)), 3-(3,5-dichlorophenyl)-N-(1-methylethyl)-2,4-dioxo-1-imidazolidinecarboxamide (hereinafter, referred to as the Compound (III)) and 3-(3,5-dichlorophenyl)-5-methyl-5-vinyl-1,3-oxazolidine-2,4-dione (hereinafter, referred to as the Compound (IV)); and
the pyrazolinone derivative (hereinafter, referred to as the Compound (I)) represented by Chemical Formula: 
xe2x80x83wherein
R1 represents halogen or methyl optionally substituted with halogen, R2 represents hydrogen, halogen or methyl optionally substituted with halogen, R3 represents isopropyl, sec-butyl, 1-ethylpropyl, 1-methylbutyl, tert-butyl or 1,1-dimethylpropyl, R4 represents oxygen or sulfur and R5 represents C1-C5 alkyl, C2-C5 alkynyl or C3-C5 alkenyl;
as active ingredients.
And also it provides a method (hereinafter, referred to as the method of the invention) for controlling plant diseases by applying at least one imide compound selected from the Compound (II), the Compound (III) and the Compound (IV); and the Compound (I); to plant(s), to land where plant(s) is growing or to seeds of plant.
At first the Compound (I) is described.
In the definition of R1 and R2 in the Chemical Formula (I); halogen includes fluorine, chlorine and the like, methyl optionally substituted with halogen includes methyl, trifluoromethyl, trichloromethyl and the like. In the definition of R5; C1-C5 alkyl includes methyl, ethyl, propyl, butyl and the like, C2-C5 alkynyl includes 2-propynyl, 2-butynyl, 3-butynyl and the like, C3-C5 alkenyl includes 2-propenyl, 2-butenyl, 3-butenyl and the like.
Preferred compounds among the Compound (I) is the compound wherein R1 is chlorine, R2 is chlorine, R3 is sec-butyl, R4 is sulfur and R5 is ethyl.
The compound represented by Chemical Formula (I) can exist as tautmers represented below. In this description, xe2x80x9cthe Compound (I)xe2x80x9d extends all of these tautmers. 
While sometimes streoisomers originated from (a) double bond(s) or from (an) asymmetric carbon(s) may exist in the compound represented by Chemical Formula (I), xe2x80x9cthe Compound (I)xe2x80x9d extends to all of these streoisomers and the mixtures of at least two these stereismers.
Examples of the Compound (I) are listed in Table 1 together with compound numbers.
In Table 1, xe2x80x9cMexe2x80x9d represents methyl, xe2x80x9cEtxe2x80x9d represents ethyl, xe2x80x9csec Buxe2x80x9d represents sec-butyl and xe2x80x9ciso Prxe2x80x9d represents isopropyl. And a symbol of (+) in the compound number indicates that the compound is a optically active substance which shows plus optical rotation (solvent: methanol). A symbol of (xe2x88x92) in the compound number indicates that the compound is a optically active substance which shows minus optical rotation (solvent: methanol).
Next, a Production Example for the Compound (I) are described below.
Step (1)
Zero point nine eight (0.98) g (3.29 mmol) of bis(trichloromethyl)carbonate was dissolved in 10 ml of 1,4-dioxane, to which 0.79 g (10.0 mmol) of pyridine was added dropwise under cooling with water. After stirring at room temperature for 30 minutes, 1.35 g (10.0 mmol) of 2-propene-1-thiol was added dropwise, and additional 30-minutes stirring at room temperature, the reaction solution was filtered to obtain a filtrate (hereinafter, referred to as xe2x80x9cfiltrate Axe2x80x9d).
Step (2)
Three hundred (300) ml of 3N hydrochloric acid and 100 ml of ethanol were added to 107 g (313 mmol) of 3-amino-2-tert-butyl-1-isopropyl-4-(2,6-dichlorophenyl)-3-pyrazoline-5-one and stirred under the refluxing condition for 4 hours. Then ethanol was distilled off under reduced pressure and the aqueous layer was neutralized with a dilute sodium hydroxide solution. The precipitated solid was filtered out, washed with water and ethyl acetate, and dried in vacuo to obtain 88.4 g (309 mmol) of a compound described below. 
3-Amino-2-tert-butyl-1-isopropyl-4-(2,6-dichlorophenyl)-3-pyrazorine-5-one can be prepared according to the method(s) described in JP-A-8-208621.
Step (3)
Twenty (20) ml of toluene was added to a mixture of 1.41 g (4.93 mmol) of the compound obtained at step (2) and 0.42 g (10.0 mmol) of lithium hydroxide monohydrate, and the mixture was refluxed for 30 minutes while removing water by azeotoropic dehydration. Then toluene was distilled off under reduced pressure and 10 ml of 1,4-dioxane was added to a residue. The xe2x80x9cfiltrate Axe2x80x9d obtained at step (1) was added dropwise under the refluxing condition, and after additional 10-minute stirring under the refluxing condition, 1,4-dioxane was distilled off under reduced pressure. Water was added to a residue, the solution was extracted with ethyl acetate, and the organic layer was washed twice with water. Then the solvent was distilled off under reduced pressure and a residue was subjected to silica gel column chromatography to obtain 0.14 g (0.36 mmol) of the Compound (I-o).
m.p.: 170.80xc2x0 C.
The Compound (I) except the Compound (I-o) can be prepared according to the method described above.
It is known that N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide was as its common name of xe2x80x9cprocymidonexe2x80x9d, 3-(3,5-dichlorophenyl)-N-(1-methylethyl)-2,4-dioxo-1-imidazolidinecarboxamide as its common name of xe2x80x9ciprodionexe2x80x9d and 3-(3,5-dichlorophenyl)-5-methyl-5-vinyl-1,3-oxazolidine-2,4-dione as its common name of xe2x80x9cvinclozolinxe2x80x9d. And these compound are commercially available compounds, described in the catalog of Farm Chemicals Handbook, 1999, C-318 (procymidone), C-224 (iprodione) or C-407 (vinclozolin). Preferred compound among these imide compounds is procymidone.
The present invention can control a variety of plant diseases, examples are described below. In the method of the invention, usually the composition of the invention is applied.
Blast (Pyricularia oryzae), Helminthosporium leaf spot (Cochliobolus miyabeanus) and sheath blight (Rhizoctonia solani) of rice plant; powdery mildew (Erysiphe graminis), scab (Gibberella zeae), rust (Puccinia striiformis, P. graminis, P. recondita, P. hordei), snow blight (Typhula sp., Micronectriella nivalis), loose smut (Ustilago tritici, U. nuda), bunt (Tilletia caries), eyespot (Pseudocercosporella herpotrichoides), scald (Rhynchosporium secalis), leaf blight (Septoria tritici) and glume blotch (Leptosphaeria nodorum) of barley, wheat, oats and rye; melanose (Diaporthe citri), scab (Elsinoe fawcetti) and pencillium rot (Penicillium digitatum, P. italicum) of citrus; blossom blight (Sclerotinla mali), canker (Valsa mali), powdery mildew (Podosphaera leucotricha), Alternaria leaf spot (Al ternaria mali) and scab (Venturia inaequalis) of apple; scab (Venturia nashicola, V. pirina), black spot (Al ternaria kikuchiana) and rust (Gymnosporangium haraeanum) of pear; brown rot (Scierotinia cinerea), scab (Cladosporium carpophilum) and Phomopsis rot (Phomopsis sp.) of peach; anthracnose (Elsinoe ampelina), ripe rot (Glomerella cingulata), powdery mildew (Uncinula necator), rust (Phakopsora ampelopsidis), black rot (Guignardia bidwelii) and downy mildew (Plasmopara viticola) of grape; anthracnose (Gloeosporium kaki) and leaf spot (Cercospora kaki, Mycosphaerella nawae) of Japanese persimmon; anthracnose (Colletotrichum lagenarium), powdery mildew (Sphaerotheca fuliginea), gummy stem blight (Mycosphaerella melonis), stem rot (Fusarium oxysporum), downy mildew (Pseudoperonospora cubensis), late bright (Phytophthora sp.) and damping-off (Pythium sp.) of melons and cucumbers; early blight (Alternaria solani), leaf mold (Cladosporium fulvum) and late blight (Phytophthora infestans) of tomato; brown spot(Phomopsis vexans) and powdery mildew (Erysiphe cichoracearum) of eggplant; altenaria leaf spot (Alternaria japonica) and white spot (Cercosporella brassicae) of vegetables of Cruciferae; Welsh onion rust (Puccinia allii); purple stain (Cercospora kikuchii), Sphaceloma scab (Elsinoe glycines) and pod and stem blight (Diaporthe phaseolorum var. sojae) of soybean; kidney bean anthracnose (Colletotrichum lindemthianum); early leaf spot (Cercospora personata) and leaf spot (Cercospora arachidicola) of peanut; pea powdery mildew (Erysiphe pisi); early blight (Alternaria solani) and late blight (Phytophthora infestans) of potate; strawberry powdery mildew (Sphaerotheca humuli); net blister blight (Exobasidium reticulatum) and white scab (Elsinoe leucospila) of tea plant; brown spot (Alternaria longipes), powdery mildew (Erysiphe cichoracearum), anthracnose (Colletotrichum tabacum), downy mildew (Peronospora tabacina) and (Phytophthora nicotianae) of tobacco; beet leaf spot (Cercospora beticola); black spot (Diplocarpon rosae) and powdery mildew (Sphaerotheca pannosa) of rose; leaf spot (Septoria chrysanthemi-indici) and white rust (Puccinia horiana) of chrysanthemum; gray mold (Botrytis cinerea) and stem rot (Sclerotinia sclerotiorum) of various crops and the like.
And also the composition of the invention can effectively control the fungi (plant diseases) which are tolerant to the imide compound such as procimidone, iprodione or vinclozolin.
In the composition of the invention, a weight ratio of at least one imide compound selected from the Compound (II), the Compound (III) and the Compound (IV), to the Compound (I), is usually 0.5 to 8:1, preferably 1 to 2:1.
In the case of applying the composition of the invention for the method of the invention, it is no problem applying merely a mixture (hereinafter, at least one imide compound and the Compound (I) together are referred to as the active ingredients of the invention) of at least one imide compound selected from the Compound (II), the Compound (III) and the Compound (IV), and the Compound (I), without other ingredient. But usually the composition of the invention may be applied in the form of formulations such as emulsifiable concentrates, flowables, granules, dry-flowables, wettable powders, aqueous liquid formulation, oil solution, smoking formulation, aerosol, micro capsule and the like which can be prepared by mixing the active ingredients of the invention with solid carriers, liquid carriers, gas carriers, surfactants and the like, and if necessary, adding other adjuvants such as adhesive agents, dispersing agent, stabilizers. In such a formulation, the active ingredients of the invention are usually included at the total amount of 0.1% to 99% by weight, preferably 0.2% to 90% by weight.
The solid carrier to be used in the formulation may include, for example, the following materials in fine powder or granule form: mineral materials (e.g., kaolinite clay, attapulgite clay, bentonite clay, montmorillonite clay, acid clay, pyrophyllite, talc, diatomaceous earth, calcite), natural organic materials (e.g., stalk of corn, powder of wallnut-shell), synthetic organic materials (e.g., urea), salts (e.g., calcium carbonate, ammonium sulfate) and synthetic inorganic materials (e.g., synthetic hydrated silicon oxide). The liquid carrier may include, for example, aromatic hydrocarbons (e.g., xylene, alkylbenzene, methylnaphthalene), alcohols (e.g., isopropyl alcohol, ethylene glycol, propylene glycol, ethylene glycol mono-ethyl ether), ketones (e.g., acetone, cyclohexanone, isophorone), vegetable oils (e.g., soybean oil, cotton seeds oil), petroleum aliphatic hydrocarbons, esters, dimethyl sulufoxide, acetonitrile and water. The gas carrier may be include, for example, LPG (e.g., butane, propane), nitrogen, carbon dioxide. The surfactant may include, for example, anionic surfactants (e.g., alkylsulfate ester salts, alkyl(aryl)sulfonic acid salts, dialkylsulfosuccinic acid salts, phosphate salts of polyoxyethylenealkyl aryl ether, lignin sulfonic acid salts, naphthalenesulfonic acid formaldehyde condensations), nonionic surfactants (e.g., polyoxyethylene alkyl aryl ethers, polyoxyethylene propylene block copolymer, sorbitan fatty acid esters). The other adjuvants may include, for example, water-soluble polymers (e.g., polyvinyl alcohol, polyvinylpyrrolidone), polysaccharides (e.g., gum arabic, alginic acid and their salts, CMC (carboxy methyl cellulose), xanthan gum), inorganic materials (aluminum magnesium silicate, alumina sol), preservatives, coloring agents, PAP (isopropyl acid phosphate), BHT.
The composition of the invention can also be prepared by formulating each the active ingredient of the invention into an formulation with the style described above, and if necessary after diluting with water, and mixing the formulations separately formulated or the dilutions separately diluted.
The method of the invention, in which the composition of the invention is applied, is not limited to specified methods, when the composition of the invention can be substantially applied; for example, treatment of plant(s) such as foliar treatment, treatment of land where plant(s) is growing or will grow such as soil treatment, treatment of seeds of plant such as seeds disinfecting.
In the method of the invention, the application amount of the active ingredients of the invention; although it may vary with a variety of plants (crops) to be protected, a variety of plant diseases to be controlled, a extent of disease damage, a formulation type, an application type, application times, weather condition and the like; is usually 0.1 to 50 g per are, preferably 1 to 10 g per are. In the active ingredients of the invention, a weight ratio of at least one imide compound selected from the Compound (II), the Compound (III) and the Compound (IV), to the Compound (I), is usually 0.5 to 8:1, preferably 1 to 2:1.
In the case of emulsifiable concentrates, wettable powders, flowables and the like, they are usually applied after diluted with water, usually at a concentration of 0.0005% to 2%, preferably at a concentration of 0.005% to 1% as active ingredients of the invention. In the case of dust formulations, granules and the like, they are usually applied as it is without diluting. In the case of treatment of seeds, a amount of the active ingredients of the invention is usually 0.001 to 100 g per 1 kg of seeds, preferably 0.01 to 50 g per 1 kg of seeds.